Valuable co-products derived from fractionation of alfalfa herbage give the resulting fibrous fraction an economic advantage as a feedstock for ethanol or other organic products. Alfalfa fiber was saccharified and fermented with or without a liquid hot water (LHW) pretreatment. The LHW pretreatment hydrolyzed approximately 60% of the original fiber, yielding a high cellulose residue and a liquid extract. These yielded predominantly hexoses and pentoses, respectively, after enzymatic saccharification. Yields of ethanol and lactic acid resulting from fermentations are given.